Process of making wool-like cellulosic textile materials



MAKING WOOL-LIKE CELLULOSIC TEXTILE MATERIALS assignor to E. I. du Del., a

PROCESS OF Hugh C. Gulledge, Newark, Del.-,

Pont de Nemours and Company, Wilmington, corporation of Delaware No Drawing. Filed Jan. 9, 1958, Ser. No. 707,857 9 Claims. (Cl. 8- 117) This invention relates to the production of novel, cellulosic materials exhibiting modified properties, and more particularly to the preparation of improved fibrous cellulosic materials adapted for use in the textile industry.

Differences in the properties of wool and cotton fibers and textiles are well known in the trade and it is well recognized that a fiber possessing the properties of cotton together with the crease resistance of wool would provide a valuable product adaptable to wide and extensive usage.

For instance, such material could be advantageously.em-

ployed in mens light-weight suits for summer wear while presenting an appearance comparable to the warmer woolens, and in the manufacture of womens clothes since a dressy appearance would be desirably assured for substantial periods in warm and humidweather; Although heretofore many treatments have been devised and proposed, the. impartation of satisfactory crease-resistance i United States Pfl fi o characteristics of the textile material and not-subject: to 5/ change or modification even when recourse to relatively expensive treatments is had. N This application is a continuation-in-part of my copending application Serial No. 474,586, filed December 10, 1954, now abandoned; I

In my copending application, novel highly usefulcellulosic textile materials are disclosed which'advantageously' possess wool-resembling properties as well as a novel combination of other desirable characteristics, including increased liveliness, crease, mildew, abrasion and flame I resistance, greater warmth and insulating characteristics,

together with improved washability and highymelting point. Also disclosed are novel methods for'converting such inexpensive typecellulosic materials to more;usef,ul

products competitive with wool and syntheticfiberssuch as nylon polyamidecondensation-polymer and Orlon acrylonitrileaddition-polymer, p, by treating a cellulosic material with a swelling and conditioningIaghi retwting the swollen cellulosic product with a metal ester in a subas separate anhydrous solutions in sequential order. and

stantially non-aqueous environment'and preferably in the 'fie'de'ellulosic product is preparedby. wetting a suitableu cellulosic material, such ascotton or rayon, in.asubstantially a h usi sa s i -e m sx n a nt presence of said agent, regeneratingthe cellulose product by ;treatnient with aqueous rnedia; iand; separating .and

ethylene diamine. Upon desired pre-swelling, conditioning or complexing being attained, excess swelling agent is drained or otherwise removed from the swollen, complexed amine cellulose product, and it is then immersed in a solution of an anhydrous organic metal ester, especially of a metal of the fourth group of the periodic table, e.g., alkyl or aryl metal esters of the ortho type, until the metal becomes transferred from the solution to the cellulose to form a highly tendered metal esteramine cellulose intermediate compound. This product is then separated from the organic liquid, treated with water or other aqueous media, such as water-containing organic solvents, e.g., water and alcohol solutions, or dilute aqueous media, and recovery iseffected of the improved, modified material of greater usefulness which will be found to retain substantially the macroscopic shape and geometric character of the original cellulose fiber and will be crease and wrinkle resistant.

It has been found that, in accordance with this invention, products'derived from the invention of my 'said co-pending application can'be effectively and advantageously improved, particularly in respect to desired tensile strength and fade resistance properties, if in their preparation a plurality of substantially anhydrous organic metal esters, more especially mixed esters comprising those of antimony and a metal from the fourth group of the periodic table, such as titanium or zirconium, are employed.

Accordingly, it is among the objects of this invention to provide such improved, modified cellulosic products and novel methods for effecting their preparation. Par:

ticular objects of the invention include: the provision of improved stable, fibrous cellulosic materials adaptable for use in the textile field; of products exhibiting enhanced J wool-like characteristics and which are crease and wrinkle resistant; .the provision ofa product of this character which is suitably stabilized against loss of tensile strength due to aging or photodegradation, and which is free from any obtionable tendency toward tenderizing or fading as a result of exposure to ultraviolet light. Other objects and advantages will be apparent from the ensuing descrip tion of. the invention.

In practically adapting the invention, cotton, rayon or other suitable cellulosic material to be modified is sub jected to wetting treatment in a substantially anhydrous, pure liquid amine conditioning agent until desired swelling thereof is effected. Excess of the amine'treating agent is removed from'the resulting swollen, complexed amine cellulose product, following which it is immersed for re action at an elevated temperature in a' solution of ,the contemplated mixed anhydrous meta-l] esters, .one of which comprises a hydrolyzableester of antimony,"e.g., alkyl' ors-aryl metal-esters of thebflhotype, and until the metals of said esters become transferred from the solution "to the cellulose and a highlyjtendered metallized ester amine cellulose intermediate, compound is formed.

If desired, the metal esters can be added to .the cellulose as a mixed solution in an anhydrous organic solvent ,or

while the" cellulose remains wetted by-the conditioning agent. Preferably, the metal esters used comprise the trialkyl' antimonites, such as trimethyl, triethyl, tripropyl, or tributylfiantimonite,etc., "or mixtures-thereof, and titanium or zirconium o'rtho esters, such ;as tetraalkyl tetrapropyl, tetrabutyl titanate orzirc'onate, etc), or various mixtures thereof. Upon formation of said 'interm'edi ate compound,.it' is separatedfrom them-ganic liquid,-

treated witha'queous media as contemplated in my =aforesaid copending application;andrecoveryis then;;efl'ected of 'the'improved modifie'd'product-v of this invention.

2 To; ajclearer understanding-of the inventioii-ythe fol V 3 lon'ring specificex-amples are given. "These are merely illustrative and not in limitation of said invention.

EXAMPLE I '35 grams of 2.85 oz. boiled otf cotton fabric was dried "inair at7l10 C. for two hours and then placed in-a con- ;ventional type vessel equipped with a reflux condenser and sealedtrom' the. atmosphere through a nitrogen trap. :Anhydrous monoethylamine, containing less than 1% .of

"water, was added to cover the sample. After soaking for 1 /2 hours at approximately 16 C. the liquid amine was drained from the sample and a solution, comprising 730 grams :of isopropanol, 490 grams of tetraisopropyl titanate and 8 grams of tributyl antimonite, was added. This solution, containing the sample, was heated at re- -'-fiux temperatures for two hours and then drained. The sample waswashedfree of excess metal ester and amine with several portions of anhydrous isopropanol. The washing was continued until a sample of the washings showed no cloudiness upon water addition. Water at room temperature was then added to cover the fabric and the whole allowed to stand for one hour. The fabric .was then removed and dried. The pertinent improved properties of this product are shown below in Table I.

EXAMPLE II Example I was repeated, except that the ester containing solution comprised 750 grams of isopropanol, 500 grams of tetraisopropyl titanate, and 16 grams of tributyl antimonite. The results of this treatment are also shown in Table I below.

EXAMPLE III negates TiO, and containing 200 grams of triisopropyl antimo- "nite, weread'cled. This solution was circulated through the yarn at 60 C. for l A' hours. The nitrogen blanketing vents were then closed and the solution heated at 85 C. under 25 lbs. pressure for one hour. After cooling to 60 C., the metallating solution was drained and the excess unreacted metal esters washed out of the yarn with .isopropano'liat 60 C. Water at 30 C. was then added and circulated for 30 minutes. The yarn was removed, centrifuged and dried, and woven into fabric for testing. The properties of the fabric obtained are Analysis of Fabric Relative Tear Strength After 25 DaysliO;, Sb203, Southern Ex- Percent Percent pqsure, Septtember; Grams Sample Untreated Control '1, 100 Sample treated with TP'I only 13.0 100 Example I. 13.0 2. 7 300 Example II. 11.8 4. 3 .920 Example III... 7 7. 4 9. S l. 170

i1 Example I ..except no antimonite was present.

I (The relative tear-strength data given inTable I above which could be-pulled away from the scale by hand. By

'pullingthe split stripin this manner a nine inch tear was made and the.load:during tearing was read from the scale in grams. The differencein magnitude of the figures given in Tables Iand:II is due to a difierent type of fabric, of stronger characteristic, used in Table II.)

' I E MPLE .Iv

' Alb. skeins 0140/2 ply grey cotton yarnwere'packed 'cont'aining'product of Example II.

in baskets and dried inan oven-at-llO C; for 2 hours. v

in a dyeing machine and blanketed with dry nitrogen. Thi dyeing machinewas equipped to treat the yarn with a The basketscontaining the 'dried yarn werexthen placed .70 a l quid, either-at atmospheric pressures or somewhat elevated pressures. Anhydrous; :monoethylamine was circulated through the yarn-.fortone, hour at 3C. The

free aminewas-jdrained olf'and'SIgallons of a solution 1 qtitetraisoprgpyl titanate rin isopropanol, analyzing 921% shown in Table II below.

EXAMPLE V Example IV was repeated, except that the titanating solution used comprised 5 gallons of an isopropanol solution of tetraisopropyl titanate, containing 9.3% TiO plus 400 grams of isopropyl antimonite. Tests on the fabric treated in accordance with this example are shown in Table II below. EXAMPLE VI Example IV was repeated except that a titanating solution comprising 5 gallons of an isopropanol solution .of tetr'aisopropyl titanate analyzing 9.6% TiO and 700 grams of triisopropyl antimonite Was used. Tests on the resulting fabric from this example are also given in Table II'below.

EXAMPLE VII Example IV Was repeated except that a titanating solution comprising 5 gallons of an isopropanol solution of tetraisopropyl titanate analyzing 8.5% TiO and 1400 grams of triisopropyl antimonite was used. Table II below also shows the properties of the fabric obtained vin this example. Y

H (The crease test used in this table is designed to measure the ability of the fabric to recover from creasing or wrinkling, and is described in Technical Bulletin #T-7, published December 1, 1947 of Monsanto Chemical Company.) a

. 7 EXAMPLE VIII Example I was repeated, except that an ester containing solution, comprising 750 grams of'isopropanol, 500 grams of tetraisopropyl zirconate and 16 grams of tributyl antimonite was employed. The final product analyzed 12% ZrO and 4.2% SbO The relative tear strength was'tested asin Examples I to III, and the prod: not was determined to be slightly better than the titanium 7 The modified cotton fabric was-crease resistant'and had wool-like properties;

I 7 EXAMPLE IX A treatment similar to-that carried out in'Example III was efi'ectedfbut' with a sequential contact ofthe-fabric witha'. separate titanium ester solution'a nd witha-separate-antimony' ester' solution, instead or throughthe simultaneous contact of a combined solution of the metal esters fas =u'sed iniExample 111. They fabric..'wasf "first immersed in a ,tetraisopropyltitanate solution consisting of 750-gramsot isopropanol andSOO grains .of the "titanate -and maintainedjtherein at a temperature of C. rep-twehours with mildjagitation. Subsequently, the

es s as will be shown below. The metal ester can be added This treatment was also continued'for two hours at 80 C. as before. The fabric was removed, rinsed with isopropanol, dried, analyzed and tested as in the instance of Example III. The results obtained were similar to those shown in Table I for the product from Example HI. The fabric possessed improved crease resistant properties and relative tear strength after 25 days Southern Exposure better than the untreated control, a TiO content of 7.6% and a Sb O content of 9.9%.

Although described and illustrated above as applied to certain specific embodiments, the invention is not to be considered as limited thereto. Hence, while particular temperatures, times, pressures, reactants, ratios, concentrations, etc., have been used, these can be suitably varied without departing from the spirit and scope of the invention. Thus, in the metallation step, temperatures ranging from about room (25 C.) to 150 C., or higher, and preferably from about 40 C. to 100 C. can be resorted to, as can relatively short or long, say, up to 24 hours, reaction time periods. In general, at higher temperatures, relatively short periods are required, while longer periods are necessary when lower temperatues are used, with the time and temperatures employed controlling the extent of cellulose effected. When employing relatively prolonged reaction periods at high temperatures, it will be found desirable to blanket the reactants with an inert gas, such as nitrogen, argon, helium, etc., in order to exclude oxygen or like undesired gasespresence so that any tendency toward degradation of the final cellulose product will be avoided. The pressures utilized can range from atmospheric to any extentrequired to maintain the desired liquid condition, e.g., up to the vapor pressure of the solution, solvent, amine and metal ester mixture used at the temperature employed. Again, complexing agents especially useful herein comprise any nitrogenous swelling agent such as ammonia and amine-nitrogen compounds containing a '--NH or NH radical. Examples thereof include short chain or small ring primary or secondary monoor polyorganic ammonia derivatives. Liquid anhydrous NH ethyl amine, methyl amine, ethylene diamine, and diethylene triamine are especially useful and effective. Other useful agents include hydrazine, formamide, urea, phenyl urea, thio urea, isopropyl amine, propylene diamine, triethylene tetramine, trimethylene tetramine, dimethyl amine, Nacetyl methylamine, diethylene amine; difunctional short chain amine derivatives such as ethanol: amine, 1,3-diaminopropanol-2, aminoethyl ethanolamine, etc. These reactive nitrogenous reagents, known for their ability to swell cellulose, have proved effectively useful and can be used in pure state, being added to and caused to react with substantially anhydrous cellulose under pressure and temperature conditions 3 consistent with the maintenance of amajor part of the swelling and complexing agent in the liquid state. By conditioning agents I refer to those compounds, usually swelling agents, which suitably modify the cellulose and enable -or promote reaction therewith of atitanium or other S1nce'my process is less comf contemplated metal ester. plicate'd when the' reagent. iser'nployed in'pure, liquid state, e.g., pure methyl amine or pure ethylene diamine,

I preferably resort to this form-ofreagent. If desired,

substantially non-aqueous solutions of the reagents in compatible organic solvents can also be employed. It is preferable that the amine swelling agent andals'o the However, the incidental presenceof small quantities; ofi water in either does not seriously'interfere withthe pr moresuitably, :as a solutioniin anorgarlic "solvent; such 6 dioxane, parafiin, hydrocarbon, etc. While tetraisopropyl titanate as a solution in isopropanol is preferred for use because it is one of the less expensive useful titanates from which economical recovery of the isopropanol can be effected, the invention is not limited thereto.

As already indicated, general use is contemplated in conjunction with an antimony ester of any hydrolyzable organic ester of a polyvalent metal, especially of Fourth Group metals, such as titanium or zirconium, or mixtures thereof adapted to tenderize swollen cellulose. This includes the ortho esters as well as the partially condensed esters. The ortho esters are defined by theformula M(OR) in which M includes aluminum, iron (ferric), titanium, zirconium, hafnium, thorium, etc., e.g., metals which form water insoluble oxides and have a coordination number at least one greater than the valence of the metal in the oxide form (which number is usually 6), R is a monovalent hydrocarbon or chlorinated hydrocarbon radical, such as an alkyl (methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl, isoamyl, etc.), cycloalkyl (cyclopro-pyl, cyclobutyl, cyclopentyl, etc.) aryl (phenyl, naphthyl, etc.), alkaryl (tolyl, xylyl, ethylphenyl, propylphenyl, etc.), aralkyl (benzyl, phenylethyl, phenyl propyl, etc.), and x is 3 and 4, the valence in its highest state of oxidation. For reasons of economy, esters having the smaller alkyl radicals (l-6 carbon atoms) are preferred for use, such as methyl, ethyl, propyl, isopropyl, butyl, etc. Examples thereof include the various titane ium, zirconium, hafnium, thorium, aluminum, iron tetraethylates, isopropylates, butylates, hexylates, etc., as well as-the monochloro and dichloro derivatives of these compounds. 7 ates, benzylates and naphthylates, and any ester containing a hydrocarbon radical having from l-l2 carbon atoms are satisfactorily useful. Chlorinated hydrocarbon radicals in this molecular weight range especially those ob tained. as titanates by the reaction of titanium tetrachloride upon ethylene oxide and propylene oxide are readily employable. The partially condensed titanates and zirconates usually formed by the reaction between water and the ortho esters, e.g., tetraalkyl titanates, are also useful in preparing my metallated cellulose. When these condensed esters are used, it is not necessary to have absolutely dry cellulose or amine swelling agent as starting materials. The presence of, say, afraction of a percent of water in the amine solution merely acts to polymerize a portion of the ortho ester used in the metal treating step. The degree of polymerization of the esters included in this process is preferably less than that obtained' by the interaction of an equimolar quantity of water. Similarly useful are esters containing cycloalkyl, aryl,,or ,aralkyl radicals, e.g., phenyl, naphthyLbenzyl, etc. i .Hydrolyzable antimony organic esters contemplated for use herein inconjunction' with the ortho esters mentioned are variable and can comprise antimonates and antimonites. The latter, or mixtures thereof,":are preferred ,cellulosidmaterial to be treated be substantially dry.

. 5sfan '.alcolio1, benzene, toluene,"xylene;' cyclohexane,{15

for use and'correspond to the formula (RO) Sb, wherein R is a 'monovalent hydrocarbon radical, such. as the "various'alky ls, aryls, aralkyls, cycloalkyls, mentioned above, e.g., methyl, ethyl, propyl, butyl, cycloprop'yl, phenyl, naphthyl, :tolyl, anthranyl, benzyl, xylyl, ethyl phenyl,

plienylp'ropyl, etc. and the monochloro, dichloro,-" etc., 5 derivatives of such compounds. Especially usefuliare trialkyl 'antimouites in which the hydrocarbon radical contains from 1-l2 and preferably from 1.-.6 carbon atoms.

and their-variousmixtures. Theseesters are applied under substantially anhydrous conditions, althoughthe simultaneously with the titanium or zirconium esters, ior

fiey'm' applied sequentially, e-s i ebr 'e r: he,.

However the various cyclohexylates, phenyl Examples thereof include trimethyl, ethyl, .iso-. i :propyl,::bu tyl,- 'hexyl, octyl,- benzyl, phenyltantimonites.

"Z? titanat'in'g'step, but prior to the water-washing step. Also, in' such sequentialmethodl may treat the amine swollen, titanated and water regenerated cellulose with'antirnony byre'swelling it with an amine and then treating it with an alkyl antimonite. This method serves to incorporate advantageously a maximum amount of titanium or zirconium, in the final product. Temperatures at or near the boiling'temperature of the anhydrous solvent are referred to in'the examples during the metallation treatment. Asnoted, lower temperatures may be employed and may even be preferred on commercial scale where heating and cooling equipment would be burdensome. The use of lower temperatures, say, room temperature, should be accompanied by longer contact time for the fabric and themetal ester solution.

The anhydrous metal ester is added preferably, as stated, to the cellulose while the latter is still wetted by the amine conditioning agent and the metallation is preferably carried out in the presence of suchagent. The

e'ster-amine-cellulose complex intermediate derived from reaction of the preconditioned cellulose with the ester is in severely tendered state compared to the cellulose compound-resulting from the initial swelling and complexing treatment, or compared to the initial cellulose material. That is, it is characterized by lack of strength, with the fabric tensile and tear strength-being substantially reduced, i.e. by about 10-90%, and usually to 10-30% of its original strength, and the tenacity. of yarns or fibers being reduced to a similar extent. Upon completion of the metallation, unreacted ester, amine and solvent used are drained from the intermediate with substantially anhydrous conditions still prevailing. Removal of these unreacted'rnater ialscan be further facilitated by subsequent displacementwashes, using anhydrous organic solvents, followed by draining or other physical separation methods. The anhydrous solvent-Washed ester-aminecomplexed cellulose intermediate can be used in various applications. For example, it can be immediately placed in an aqueous medium, whereupon the hydrolysis product or the intermediate is removed to leave the metal radical in reacted condition within thecellulose structure as a cellulose derivative having substantially the strength and washabilityand high melting point of the original fibrous cellulose material. Advantageously, it will possess not only the increased tensile strength and photodegradation ie'sis'ta'nt'properties mentioned above but the novel high flame, mildewresistance and single fiber characteristics of wool, includinginitial modulus, compliance ratio, work recovery, crimp el'ongation, andwool-like woven cloth properties, e.'g., handle, high crease and Wrinkle resistance shown in my said copending application. In addition, it possesses high laundering resistance, Which property and theexisting new chemical composition is retained even after' repeated washing treatments, as is also demonstrated in the disclosure of my said copending applica :tiOli.

As the above'examples and tables of testdata show, the-products from my process possess new and very desirableimprovementproperties.- In addition to their high resistance: to photodegi'adation 'and excellent wrinkle resistant and general wool-likeiproperties,they are both fiarnetresistant andmildew resistant, and thesedesirable properties are retained even after repeated 'launderin'gs, This combination of'properties gives new potential uses to' cellulose fabrics, such as cotton and rayon. My novel =tfeatments also'iprovidewery marked improvements in other cellulosic'fibrousmaterials, such aslinen and ramie,

andrerid'erspossiblethe preparation of light W'ei'ghtfcom: vfoftable summer. wearing apparel from cotton and rayon, which willfh'ave wool-.likeproperties andbe. resistant to' degradationzbyisunlight. Y The'products of this inventionwill-also advantageously .retain -substantiallyfihe macroscopic shape andgeometric character ;of"-the-: original1 cellulose fiber; ey wilLbe statesiszt r ds 2., A

solutions: Inrespect to wool-like and wrinkle resistance properties alone they exhibit an at-least 20% and usually 3.30% or greater improvement over untreated cotton. Prior art products give very low wrinkle resistance as measured by hand test or by the crease tester method referred ,to in'my said copending application. Although the fibers resulting from my novel treatment have an increased fiber density value substantially as would be expected due to metallation, the bulking value, i.e. vol./wt. ratio is uniquely increased. This characteristic along with enhanced elasticity whichis indicated by elongation at the break point, demonstrates that wool-like properties, in addition to crease resistance, are attained by my process. 7

As already indicated, it is unnecessary to effect removal of substantially all of the amine swelling agent from the cellulose prior to the metallation treatment. In fact, the presence of the amine in some concentration during such step will be found to enhance the ultimate metallation effected. Thus, for example, the metallation can be carried out with an isopropanol solution containing approximately 18% .by weight of tetraisopropyl titanate, 15% of isopropyl antimonite and 15% of ethyl amine. As little as 2 "or 3% of the amine will be noticeably eifective,v lith somewhat higher (above, say l5 being also satisfactory for use. Since a substantially 15% concentration of ethyl amine or-its equivalent yields optimum results hereunder, a 5-15% range amount is preferred for use.

While the examples illustrate the invention as applied to the treatment of woven fabrics, yarnsand staple, the invention has utility in modifying the properties of nonwoven'textiles. It has general application to any hydroxyl-containing derivative of cellulose, including commercial wood pulp,'-paper, cellulose,-ce llul0se sponge, cupra-ammonium rayon, commercial cellulose acetate, mercerized cotton, and regenerated viscose in the form of fiber or cloth, etc. For example, cotton or rayon staple may be readily immersed in one of the organic conditionin'g agents mentioned, separated from the non-absorbed agent and immersed in the anhydrous liquid mixed metal ester composition. Thereafter, it is separated from:

the organic liquids, Washed with water, and dried. During thisoperation the cellulose, whether it be cottonror a regenerated cellulose rayon, or a hydroxyl-containing derivative of cellulose, becomes modified by such composition to result in a cellulosic material containing from about 2% up to 40% or more of the mixed metals, calculated as oxides inchemical combination with the cellulose. Normally, the products of the invention will contain from about 535% of said'metal oxides, and, preferably; from about l0-30%' thereof. As noted, use has be n had of elevated-or boiling temperatures inthe reaction'of the metal esters'with the cellulose material in the-examples. However, this is not considered essential to the beneficial results'jof the invention The reaction can be accomplished at lower temperatures through employment of longercoutact' times at the discretionof the operator. The temperature used in removal of solvents after completion of the reactions is likewise flexible, and one can employ any suitable vaporization conditions The variable reaction times, tempertature, pressure of the.

. systemgwhen swelling and complexing-as well as when reacting and tenderizing the swollen and complexed product'by;ester treatment, -are as already indicated dependent of subsequent metallization or degree of change of physi- [cal and chemical properties to be effected or desired. (70.

Where relatively low-boiling liquids are used, such, as anhydrous ammonia or.methylamine, either low temperatiire operation at atmospheric (pressure, or higher temperatureloperation atia pressure sufiicient to maintain h i I-PQ QB flammea d i t e nit s l ui an w sqa a f a newnplexingsteps "are also advantageous"'and effective. A' minimum of about 30 minutes of contact is preferred in the first step, that is, in swelling and complexing the cellulose with the ammonia derivative; while a minimum of about 15 minutes is preferred in the second complexing or tenderizing step when addition and reaction of the ester with the complexed cellulose is effected. The reaction of the ester-ammonia-derivative-complexed cellulose intermediate with water depends on penetration, with a period of about 15 minutes to an hour at room temperature being preferably employed in this step.

The final product from this invention will advantageously contain not more than a trace of nitrogenous material and appreciable quantities of the titanium or zirconium and antimony. .The relative amounts and total amounts of titanium and antimony present are not especially critical, but optimum results with respect to woollike, wrinkle or crease resistant properties and resistance to photodegradation and'dye fading will be found to occur when the finished, dried product contains between about and 30% of the combined oxides, TiO; and

I Sb O and when such oxides are present in a weight ratio ranging from about .3 to 5. The preferred values lie roughly at 20% of combined oxides with approximately equal weights of TiO and Sb- O present according to analysis. The mol ratio of MO /Sb O therefore, lies in the range of about 1 to 10 and is preferably about 3 to 4, where M is either titanium or zirconium.

As indicated above, the invention yields a modified cellulosic textile material having the crease resistance and resilience approaching that of wool. Upon release after pressing, the fibers and textile will readily spring apart, a characteristic known as recovery. These attributes assure production of a material having desired loft (high bulk or volume for a given weight) properties which afford ready production of wool-like, open, porous fabrics of high covering power and thick, warm fabrics with a enhance its value for acceptance by textile manufacturers and the garment industry.

During the contemplated treatments and reaction, the

' strength of the cellulose material undergoing modification becomes poor and fabrics such as used-in the. examples lose strength to such an extent that they are easily damaged by punctures and tears. It is believed that the cellulose is degenerated under the conditions of the process by a breaking of the cross-linkage'of cellulose. The antimony and titanium, or other metal, enters into chemical combination with thecellulose and-the anhydrous product has poor strength. due to this lack of crosslinkage between molecular units of the cellulose fiber. Upon treatment and regeneration with jwater,however, there is strong evidence thatcross-linkage again takes place to cause the fabric to resume .itsoriginal tensile 10 accordance with the following procedure outlined in my concurrently filed copending application Serial No. 707,870, with all processing from the drying to the final product being effected under dry nitrogen to eliminate moisture pick-up.

The existence of a chemical combination of the treating metals with the cellulose is also evident from the excellent mildew resistance which the metallated, especially the antimonited and titanated cellulose product exhibits, as well as from the fact that such a result is not obtained when recourse to precipitation of TiO in a cellulosic fabric from an aqueous solution of compounds of the metals is undertaken.

I claim:

1. A method for preparing a cellulose textile material possessing substantially the single fiber, liveliness, crease resistance and bulk characteristics of wool, comprising reacting a cellulose textile material under anhydrous conditions in the presence of a nitrogenous chemical swelling agent for cellulose selected from the group consisting of ammonia and amine compounds which swell the cellulose and form nitrogenous complexes with the cellulose and containing a radical selected from the group consisting of -NH and NH, with (l) a wa er bydrolyzable antimony ester corresponding to the formula (RO) Sb in which R is selected from the group consist; ing of a hydrocarbon and chlorinated hydrocarbon radical, and (2) a water hydrolyzable organic compound selected from the group consisting of (a) a metal ester corresponding to the formula Me(OR) wherein Me is a metal selected from the group consisting of titanium, zirconium, hafnium, thorium, aluminum and iron and which forms a water-insoluble oxide and has a valence selected from the group consisting of 3 and 4 and has a coordination number in the oxide state at' least one greater than the valence, R is selected from the'group consisting of hydrocarbon and chlorinated hydrocarbon radicals, and x corresponds to the valence of the metal, and

(b) a condensed ester of said hydrolyzable metal ester resulting from the reaction of said ester with water,

continuing said reaction until a highly tendered metal ester-amine cellulose complex intermediate product forms of substantially reduced tensile and tear strength over that of the swollen cellulose textile obtained from said chemical agent treatment, contacting said metal ester-amine cellulose complex intermediate product with aqueous media consistingessentially of water which regenerates and restores said product to substantially the tensile strength of the original untreated cellulose textile mate- .Qrial, and recovering the resulting chemically modified acting a cellulose textile material under anhydrous conditions inthe' presence of an alkyl amine chemicalswelling agent forcellulose which swells the cellulose and strength. The cross-linkage-at this-time is believed to be somewhat differentandanewchemical bonding-takes place through the antimony and titaniumor other treating metal which has entered into the, complex, structure. The improved properties are believed to be due in large measure vto this new cross-linkage or bonding {of both units of the cellulose structure; When subjected to normal washing treatment, the product-willbe foundgtobesubstantially nitrogenfree, indicating'that afrelatively 1 pure metal-modified cellulosic material has been obtained.

' That a chemical reaction and, new. chemical combina- :';tion is obtained in the "inventioneis .readilyifevidenced from the results Qbiained when, an alkyl antimonite and titanate are reacted with amine-swollen;ccllulosetsand forms nitrogenous complexes with cellulose, with (l) a fw ater, hydrolyzable antimony ester, corresponding to the formula (RO) Sb in which R isselected from the group consisting, of a hydrocarbon and chlorinated hydrocarbon radical, and (2) a water hydrolyzable, organic titanium ester corresponding to the formula Ti(OR)4 in which -R is selected-from the group consisting of hydrocarbon and chlorinatd hydrocarbon radicals, continuingsaidreaction until 'a highly tenderized metal ester-amine cellulose-com: plex intermediate is obtained having a substantially reducedtensile and tear strength compared to theiSwollen cellulose textileobtained fromsaid chemical agent treatment, subjecting said ten'derize'd metal'ester-amin e cellulose' complex"irit erinediate to contactiwith aqueous-media consisting essentially of water-which regenerates and restores :v aidcellulose intermediate to*substantially "the "immersing a cellulose textile material tensile strength of the original untreated"cellulosemata rial, and recovering the resulting modified product containing in chemical combination with the cellulose" from about 2% up to 40% of the metals of said ES'EGTSyCQlCU- lated as their oxides.

3. A method for preparing a cellulose textile material possessing substantially the single fiber, liveliness, crease resistance and bulk characteristics of Wool comprising reacting a cellulose textile material under anhydrous conditions in the presence of an alkyl amine chemical swelling agent for cellulose which swells the cellulose and forms nitrogenous complexes with cellulose, with (1) a water hydrolyzable antimony ester corresponding to the formula (RO) Sb in which R is selected from the group consisting of a hydrocarbon and chlorinated hydrocarbon radical, and (2) a water hydrolyzable organic zirconium ester corresponding to the formula ZI(R) "iI1-:Whl6lfi R is selected from the group consisting of hydrocarbon and chlorinated hydrocarbon radicals, continuing said reaction until a highly tenderized metal ester-amine cellulose complex intermediate is obtained having a substantially reduced tensile and tear strength compared to the swollen cellulose textile obtained from said chemical swelling agent treatment, subjecting said tenderized cellulose compiex intermediate to contact with aqueous media con sisting essentially of water which regenerates and restores said" cellulose intermediate to 'substant'ally the tensile strength of the original untreated cellulose material, and recovering the resulting modified product containing in chemical combination with cellulose from about 2% to 40% of the metals of said esters, calculated 'astheir oxides. V I p 4. A method for preparing a cellulose textile material possessing, substantially the, single fiber, liveliness, crease resistance and bulk characteristics of wool comprising swelling a cellulose textile material by treatment under anhydrous conditions with an alkyl amine chemical swelling agent for cellulose Whch forms nitrogenous complexes with cellulose, subjecting the resulting aminetreated, swollen and nitrogenous complexed cellulose product to reaction under anhydrous conditions with (1) a water hydrolyzable antimony ester corresponding to the formula (RO) Sb' in which R is selected from the group consisting of a hydrocarbon and chlorinatedhydrocarbon radical, and (2) a water hydrolyzable organic ester cor-respond ng to the formula Me(OR) wherein Me is a metal selected from thegroup consisting of titanium,

zirconium, hafnium, thorium, aluminum and iron, and which'fornis' a water-insoluble oxide and has a valence selectedirom the group consisting fof 3 and l and coordination number in the oxide stateat le'ast one greater than the valence, R Is an alkyl radical, and x correspondls to the valence of the metal, continuing said-neaction until a' highly tendered metal estereminei cellulose complex' intermediate is obtained the" tensile; and: tear'strength of which is substantially reduce d-over'ihat of-theoriginally treated swollen cellulose textile, subjecting sa'd cellulose complex intermediate product to contact with aqueous media consisting essentially ofiwatier which regenerates and restores said cellulose intermediate "to substantially the tensile strength or the original untreated cellulose textile, and recoveringthe result ngmoclifiedjellulose product containing in chernical combination the cel: lulose from about 5% to 35% of the. metals of said esters, calculated as theiroxides. 7

5. Arnetho'd for preparing a celluloseitextileiniate r51 resistance and bulk characteristics ofv woor'comprising nh'yq'r'su "conditions in an alkyl amine ehemienswe u agent nn cellulose. which forms nitrogenous consplexes with cellulose' ';,until a swollen nitrogenous lcomplexedacellulose smaller, is obtainedflrernoving underanhydrouspondi- 1 excess -amline; reactant;-from thexswcllengcellulose .possessing substantially t e single fiber, liyeltness erease product and'immersing the latter for reaction under anhy drousconditions at temperatures ranging from-about 25 ,to 156 (2. ina-solution of (1) a water hydrolyzable antimony ester corresponding to the formula (RO) Sb in which -R-is-selected from the group consisting of a hydrocarbon and chlorinatedthydrocarbon radical, and (2) a water hydrolyzab'le organic ester corresponding to theformula' Me(OR-), wherein Me is a metal selected from the group consisting of'titaniurn, zirconium, hafnium, thorium, aluminum and iron and which forms a waterinsoluble oxideand has a valence selected from the group consisting of -3 and 4 and a coordination number in the oxide state'at least-one greater than the valence, R is an alkyl radical, andrlx corresponds to the valance of the metal, until a highly tendered 'rrietal'ester-amine cellulose complex intermediate isobtaincd with a tensile and tear strength substantially reduced over that of the amine swollen cellulose'textile, removing under anhydrous con ditions'excess or ester reactants from said tenderIzed inter mediate and immersing said cellulose complex interme diate in aqueous media consisting essentially of Water which'regenerates and restores the intermediate to substaxitially the tensile strength of the orfginal untreated cellulose textile and recovering the resulting modified cellulose product containinginchemical combination with the celliilose from about 5% to 35% of the metals of said esters, calculated as their oxides.

6. A method for preparing a cellulose textile material possessingsubs tantially the" single fiber, liveliness, crease resistanceand bulk characteristics of wool, comprising immersing ac'ellulose-textile material under anhydrous conditions in an alkyl amine chemical swelling agent for cellulose which forms nitrogenous complexes with cellulose, until a swollen nitrogenous complexed cellulose stantially the' tensile strength of the original untreated cellulose textile m'aterial, andthereafte r recoveiing'the resulting chemicallymodified cellulose product.

- 7. A method for preparing a cellulose textile material possessing substantiallythe singlefiber, liveliness, crease resistance and-bulk'chafacteristics of wool comprisingim rn'ersing a cellulose textile material under anhydrous conditions in an alkyl aniine chemical'swellingagent for cellulose which forms nitrogenous complexes with cellulose, until a swouen'nitrbgencsus com lexes cellulose product-is"obtained, removing under anhydrous conditions e cess arnine reactant from saidproduet and reacting the latter u ndelr' anhydrous conditions at tempera tu es'rangingtrorn about 40 C. to g C. ith a soletion ofwater hydrolygable tiibutylantimonite and water hydrolyzable tetraisopropyl z'irconate 7 until a highly tendered metal' ester a'niine cellulose com le intermediate s'ile strength tear strength isfiobta ined having a te substantially reduced"at enuator i swollen cellulose textile, removing under anhydrfous conditions' excess unreacted I antimonite and I zirconate reactants frornsaid cellulosecomplex intermediate andsubjecting the latter to contact with water which reg'erzler'ates and restores" said intermediate to substantially the tensile strength of the ioriginaliuntreated cellulose textile material, and there.- after '-recoveri'ng-,the resulting chemically'iniod-ified' cel'- luloseaproductr a r r 1 8: A 'methedrm prepanng acellulose textile rnaterial possessing substantially the single fiber, liveliness, crease resistance and bulk characteristics of wool, comprising immersing under anhydrous conditions a cellulose textile material in an alkyl amine chemical swelling agent for cellulose which forms nitrogenous complexes with cellulose until a swollen nitrogenous complexed cellulose product is obtained, removing under anhydrous conditions excess amine reactant from said product and reacting the latter under anhydrous conditions at temperatures ranging from about 40 C. to 100 C. with a solution of a water hydrolyzable alkyl ortho ester of antimony and water hydrolyzable alkyl ortho ester of iron until a highly tendered metal ester-amine cellulose complex intermediate is obtained having a tensile and tear strength substantially reduced over that of the swollen cellulose textile, removing under anhydrous conditions excess unreacted antimony and iron ester reactants from said cellulose complex intermediate and subjecting the latter to contact with water which regenerates and restores said intermediate to substantially the tensile strength of the 14 latter under anhydrous conditions at temperatures ranging from about C.- C., with a solution of a water hydrolyzable alkyl ortho ester of antimony and water hydrolyzable alkyl ortho ester of aluminum until a highly tendered metal ester-amine cellulose complex intermediate is obtained having a tensile and tear strength substantially reduced over that of the swollen cellulose textile, removing under anhydrous conditions excess unreacted antimony and aluminum ester reactants from said cellulose complex intermediate and subjecting the latter to contact with water which regenerates and restores said intermediate to substantially the tensile strength of the original untreated cellulose textile material, and thereafter recovering the resulting chemically modified cellulose product.

References Cited in the file of this patent UNITED STATES PATENTS 2,009,015 Powers July 23, 1935 2,525,049 Signaigo Oct. 10, 1950 FOREIGN PATENTS 517,464 Great Britain Ian. 31, 1940 OTHER REFERENCES Balthis: Abstract No. 692,385, May 16, 1950.

Speer: Ind. and Eng. Chem., February 1950, pp. 251-253;

Gulledge: Ind. and Eng. Chem., March 1950, pp.

excess amine reactant from said product and reacting the 4 Moncrieft: Textile Colourist and Finisher, August 1950, pp. 394 and 395. 

1. A METHOD FOR PREPARING A CELLULOSE TEXTILE MATERIAL POSSESSING SUBSTANTIALLY THE SINGLE FIBER, LIVELINESS, CREASE RESISTANCE AND BULK CHARACTERISTICS OF WOOL, COMPRISING REACTING A CELLULOSE TEXTILE MATERIAL UNDER ANHYDROUS CONDITIONS IN THE PRESENCE OF A NITROGENEOUS CHEMICAL SWELLING AGENT FOR CELLULOSE SELECTED FROM THE GROUP CONSISTING OF AMMONIA AND AMINE COMPOUNDS WHICH SWELL THE CELLULOSE AND FORM NITROGENEOUS COMPLEXES WITH THE CELLULOSE AND CONTAINING A RADICAL SELECTED FROM THE GROUP CONSISTING OF -NH2 AND >NH, WITH (1) A WATER HYDROLYZABLE ANTIMONY ESTER CORRESPONDING TO THE FORMULA (RO)3SB IN WHICH R IS SELECTED FROM THE GROUP CONSISTING OF A HYDROCARBON AND CHLORINATED HYDROCARBON RADICAL, AND (2) A WATER HYDROLYZABLE ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF (A) A METAL ESTER CORRESPONDING TO THE FORMULA ME(OR)X WHEREIN ME IS A METAL SELECTED FROM THE GROUP CONSISTING OF TITANIUM, ZIRCONIUM, HAFNIUM, THORIUM, ALUMINUM AND IRON AND WHICH FORMS A WATER-INSOLUBLE OXIDE AND HAS A VALENCE SELECTED FROM THE GROUP CONSISTING OF 3 AND 4 AND HAS A COORDINATION NUMBER IN THE OXIDE STATE AT LEAST ONE GREATER THAN THE VALENCE, R IS SELECTED FROM THE GROUP CONSISTING OF HYDROCARBON AND CHLORINATED HYDROCARBON RADICALS, AND X CORRESPONDS TO THE VALENCE OF THE METAL, AND (B) A CONDENSED ESTER OF SAID HYDROLYZABLE METAL ESTER RESULTING FROM THE REACTION OF SAID ESTER WITH WATER, CONTINUING SAID REACTION UNTIL A HIGHLY TENDERED METAL ESTER-AMINE CELLULOSE COMPLEX INTERMEDIATE PRODUCT FORMS OF SUBSTANTIALLY REDUCED TENSILE AND TEAR STRENGTH OVER THAT OF THE SWOLLEN CELLULOSE TEXTILE OBTAINED FROM SAID CHEMICAL AGENT TREATMENT, CONTACTING SAID METAL ESTER-AMINE CELLULOSE COMPLEX INTERMEDIATE PRODUCT WITH AQUEOUS MEDIA CONSISTING ESSENTIALLY OF WATER WHICH REGENERATES AND RESTORES SAID PRODUCT TO SUBSTANTIALLY THE TENSILE STRENGTH OF THE ORIGINAL UNTREATED CELLULOSE TEXTILE MATERIAL, AND RECOVERING THE RESULTING CHEMICALLY MODIFIED CELLULOSE PRODUCT. 